In my experience, yes. At least, I think it can work great for new GMs — I used it for the first game I ever GMed, and had a lot of fun doing so, and at least one of my players has gone on to do the same.
The thing about RfS, from a GM's perspective, is that it's a microsystem — it really doesn't do much for you, except act as a randomness generator and as a kind of a "seed" for the game to develop around. This can be a good thing or a bad thing, depending on what you're looking for. IMO, Roll for Shoes works best with a setting where you (and, preferably, your players) have a strong intuitive grasp of how things should work, and where you're comfortable following a "fiction first" approach.
On the other hand, if you're looking for a more simulationist system that tells you, say, how many hits with a one-handed sword an average goblin wearing ring mail can take, then RfS is definitely not for you. It's even worse suited for "gamist" folks who want their system to provide rules that are fair and balanced and must not be broken. (That doesn't mean you can't have an "outwit the GM" style game with RfS, but it only works if the GM wants to be outwitted, and is willing to let the players do so.) In fact, I'd say the main feature of RfS is that it effectively forces the players (and the GM) away from that kind of play, by making anything and everything technically possible.
Also, Roll for Shoes really doesn't hold your hand much, if at all. It may let you practice your GM skills, but it doesn't do much to teach them. (If you want a system that does hold your hand and teach you how to GM, try Dungeon World or its relatives.) Thus, I wouldn't necessarily recommend RfS for someone who's completely new to roleplaying in any form — it helps a lot if you've already seen a good GM (or several) in action, and know what you want to emulate.
In my experience, the one thing that RfS does teach (through the tried and true "jump into the deep end" method) is how to think fast on your feet and not plan too far ahead. You may have a whole storyline planned out in advance, but that plan isn't going to survive contact with the enemy, ahem, with the players (and their crazy dice rolls). Sure, you can nudge the players more or less subtly in the direction you want (general GMing tip: if you really want your players to do something specific, it may be a good idea to just tell them so), but they will come up with their own peculiar ways of getting there (or somewhere else, as it may happen).
Anyway, the one thing that I really like about Roll for Shoes, and what made me want to try it in the first place, is how easy it is to start playing it. There's no thick rulebook (or books!) to buy and wade through, or character sheets to fill out before you can play — all you need is some scrap paper, pencils, a bag of dice and some friends to play with. And, of course, a cool idea for a game. You can literally carry all that in your pocket (well, except for the friends, that is) and in your head, and be ready to run a game any time and anywhere you want.
Basically, I'd say that the best way to tell if Roll for Shoes is a good system for you is to just read the rules (all eight lines of them) and a few examples of how they can play out. If you find yourself thinking "Hey, cool, I want to try that too!", then go for it. If not, well, nobody says you have to. :)
